CN115295727A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a perovskite solar cell and a preparation method thereof, wherein the cell comprises an ITO substrate and SnO arranged in sequence 2 The electron transport layer, the perovskite light absorption layer, the passivation layer, the hole transport layer and the gold electrode layer; the passivation layer is a halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazine hydrogen). According to the invention, halogen salt substances containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazinehydrogen) are deposited at the interface between the perovskite light absorption layer and the hole transport layer to passivate shallow and deep defects, so that non-radiative recombination can be inhibited and interface charge extraction can be improved, and thus, the efficiency and stability of the device can be improved.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof.
Background
With the vigorous development of organic-inorganic hybrid perovskite materials, the device authentication efficiency reaches 25.7%. However, since the perovskite material contains mixed cations and anions, a number of disadvantageous defects are generated during the heat treatment, which undoubtedly adversely affect the efficiency and stability of the battery. Among the different types of defects involved in perovskite materials, the formation of low energy point defects is most pronounced because the formation of low energy point defects is likely to be sites for non-radiative recombination, resulting in a reduction in open circuit voltage and device efficiency. Meanwhile, due to the ionic properties and good ion migration speed of the perovskite material, charged point defects can migrate to the interface under the action of an electric field, thereby causing accelerated degradation of the light absorbing layer. Therefore, in order to obtain a high-performance and stable perovskite solar cell, it is important not only to passivate the interface defects causing non-radiative recombination inhibition, but also to effectively inhibit the migration of ions responsible for long-term stability under different environments.
To date, a number of functional molecules have been used to passivate lead-based defects. However, the inorganic ions and the inherent chemical instability of organic molecular layers limit their spread in practical applications. Therefore, there is an urgent need to develop a simple and effective strategy to deal with lead-based defects at the interface to obtain a high efficiency perovskite photovoltaic device with good long-term stability.
Disclosure of Invention
In view of the above, the present invention provides a perovskite solar cell and a method for manufacturing the same, wherein the perovskite solar cell has high photoelectric conversion efficiency.
The invention provides a perovskite solar cell which comprises an ITO substrate and SnO arranged in sequence 2 The electron transport layer, the perovskite light absorption layer, the passivation layer, the hole transport layer and the gold electrode layer;
the passivation layer is a halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazine hydrogen).
The solar cell provided by the invention comprises an ITO substrate; in the specific embodiment, the ITO conductive glass is used as an ITO substrate. And cleaning and drying the ITO conductive glass before use, and then carrying out UV surface treatment.
The solar cell provided by the invention comprises SnO 2 An electron transport layer of said SnO 2 The electron transport layer is made of SnO 2 And annealing after the solution deposition. The SnO 2 The solution is prepared from 1mLSnO 2 Diluting the colloidal dispersion liquid by deionized water by 4-7 times to obtain SnO 2 And (3) solution. SnO 2 The thickness of the electron transport layer is 20-30 nm.
The solar cell provided by the invention comprises a perovskite light absorption layer; the perovskite light absorption layer is made of (FAPBI) 3 ) 0.95 (MAPbBr 3 ) 0.05 . The thickness of the perovskite light absorption layer is not less than 100nm. The perovskite light absorption layer is prepared from a perovskite precursor solution; the preparation process of the perovskite precursor solution comprises the following steps: weighing formamidine hydroiodide, methyl ammonium bromide, lead iodide and lead bromide, dissolving in an organic solvent, fully stirring and filtering to obtain a perovskite precursor solution.
The solar cell provided by the invention comprises a passivation layer; the passivation layer is a halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazine hydrogen); the passivation layer is one or more of 4,5-dihydroimidazole-2-hydrazine hydroiodide substances, 4,5-dihydroimidazole-2-hydrazine hydrobromide substances and 4,5-dihydroimidazole-2-hydrazine hydrochloride substances. The thickness of the passivation layer is 5-20 nm.
The solar cell provided by the invention comprises a hole transport layer; the thickness of the hole transport layer is 150-220 nm.
The solar cell provided by the invention comprises a gold electrode layer; the thickness of the gold electrode layer is 65-85 nm.
The invention provides a preparation method of the perovskite solar cell in the technical scheme, which comprises the following steps:
deposition of SnO on ITO substrates 2 Precursor solution is annealed to obtain SnO 2 An electron transport layer;
coating perovskite precursor solution on SnO in a spinning mode 2 Heating the electron transmission layer to obtain a perovskite light absorption layer;
then spin-coating a passivation layer solution on the perovskite light absorption layer and heating to obtain a passivation layer, wherein the passivation layer is a halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazine hydrogen);
spin-coating a hole transport layer solution on the passivation layer to obtain a hole transport layer;
and preparing a gold electrode layer on the hole transport layer by using a vacuum evaporation method to obtain the perovskite solar cell.
The invention deposits SnO on an ITO substrate 2 Precursor solution is annealed to obtain SnO 2 An electron transport layer. The annealing temperature is 90-150 ℃, and the annealing time is 40-60 min.
The invention coats the perovskite precursor solution on SnO in a spinning way 2 Heating the electron transport layer to obtain the perovskite light absorption layer. The dosage of the perovskite precursor solution is 15-25 mu L/cm 2 The rotating speed of the spin coating is 3000-5000 rpm; the concentration of the perovskite precursor solution is 1.4-1.8 mol/mL; the perovskite precursor solution is an organic mixed solvent of a dimethyl sulfoxide solvent and a dimethyl formamide solvent, and the volume of the dimethyl formamide solvent in each unit volume of the organic mixed solvent is 4-9 times that of the dimethyl sulfoxide solvent; in a specific embodiment, the volume of the dimethylformamide solvent in the perovskite precursor solution is 4 times the volume of the dimethylsulfoxide solution.
In the invention, a passivation layer solution is spin-coated on the perovskite light absorption layer and heated to obtain the passivation layer. The passivation layer solution is prepared according to the following method: dissolving halogen salt substance powder containing heterocyclic ammonium salt cation (4,5-dihydroimidazole-2-hydrazine hydrogen) in solvent and stirring to obtain the halogen salt compound powder. Passivation layerThe concentration of halogen salt substance containing heterocyclic ammonium salt cation (4,5-dihydroimidazole-2-hydrazine hydrogen) in the solution is 10-50 mmol/mL; the solvent is isopropanol. The dosage of the passivation layer solution is 15-25 mu L/cm 2 (ii) a The rotating speed of the spin-coating passivation layer solution is 3000-5000 rpm; the temperature for heating the passivation layer solution is 90-120 ℃, and the time for heating the passivation layer solution is 5-10 min.
The invention spin-coats a hole transport layer solution on the passivation layer to obtain the hole transport layer. The hole transport layer solution was prepared as follows: adding tributyl phosphate (TBP), lithium bistrifluoromethylsulfonyl imide (LiTFSI) and bistrifluoromethylsulfonyl imide salt (FK 209Co (III)) into spiro-OMeTAD, and dissolving in chlorobenzene solvent. In a specific embodiment, the formulation of the hole transport layer solution is: spiro-OMeTAD 72.3mg/mL, tributyl phosphate (TBP) 28.8. Mu.L, lithium bistrifluoromethylsulfonyl imide (LiTFSI) 17.5. Mu.L, bistrifluoromethylsulfonyl imide salt (FK 209Co (III)) 8. Mu.L dissolved in 1mL chlorobenzene solvent. In the process of preparing the hole transport layer, the dosage of the hole transport layer solution is 10-15 mu L/cm 2 The spin coating speed is 3000-5000 rpm.
The invention provides a perovskite solar cell which comprises an ITO substrate and SnO arranged in sequence 2 The electron transport layer, the perovskite light absorption layer, the passivation layer, the hole transport layer and the gold electrode layer; the passivation layer is a halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazine hydrogen). According to the invention, halogen salt substances containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazinehydrogen) are deposited at the interface between the perovskite light absorption layer and the hole transport layer to passivate the surface defects of the perovskite light absorption layer, so that non-radiation compounding can be inhibited and interface charge extraction can be improved, and thus, the efficiency and stability of the device can be improved.
Drawings
FIG. 1 is an overall structural view of perovskite solar cells of examples 4 to 6 in which a passivation layer is prepared according to the present invention;
FIG. 2 is an X-ray diffraction image of a thin film of example 2 of the present invention, comparative example 1, 4,5-dihydroimidazole-2-hydrazine hydroiodide and lead iodide reacted alone and 4,5-dihydroimidazole-2-hydrazine hydroiodide;
FIG. 3 is an SEM image of the perovskite surfaces of comparative example 1 and example 2 of the present invention;
FIG. 4 is an ultraviolet-visible absorption spectrum of the perovskite thin film of examples 1 to 3 of the present invention and comparative example 1;
FIG. 5 is a graph of the I-V test results for different concentrations 4,5-dihydroimidazole-2-hydrazine hydroiodide passivation treatments of examples 4-6 of the present invention and the perovskite solar cell of comparative example 2.
Detailed Description
In order to further illustrate the present invention, the perovskite solar cell and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The method is adopted to prepare ITO/SnO with a passivation layer 2 Thin film structure of perovskite light absorption layer/passivation layer
Example 1
1) Cutting the ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning liquid, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain the ITO substrate.
SnO 2 Preparing a compact layer: 1mLSnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Furthermore, the solution method comprises the step of carrying out SnO 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Preparation of perovskite light absorption layer:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of dimethyl sulfoxide and dimethyl formamide, wherein the volume ratio of the dimethyl sulfoxide to the dimethyl formamide is 1:4, obtaining the concentration of the solution of 1.4mol/mL, stirring on a stirring table for 5 hours for full dissolution, and filtering the solution by using a 45-micrometer filter head to obtain a perovskite precursor solution;
2-2) taking 90 mu L of the perovskite precursor solution, dripping the solution, preheating at 70 ℃, and covering with SnO 2 Spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, dripping 150 mu l of chlorobenzene 15-20s before the spin-coating is finished, and heating on a heating table at 150 ℃ for 15min after the spin-coating.
3) Preparation of passivation layer
3-1) 10mmol of 4,5-dihydroimidazole-2-hydrazine hydroiodide powder is dissolved in 1mL of LIPA, the obtained solution is 10mmol/mL, the obtained solution is placed on a stirring table at normal temperature, the stirring is carried out for 2 hours, and after the solution is fully dissolved, a 45-micron filter head is used for filtering the solution.
3-2) dropping 90. Mu.L of the perovskite solution on the perovskite light absorption layer obtained by the step 2) which has been cooled, rotating it at 4000rpm for 30s, spin-coating, and then heating it on a heating stage at 100 ℃ for 5min.
The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 Perovskite material), passivation layer (4,5-dihydroimidazole-2-hydrazine hydroiodide).
Example 2
1) And cutting the ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning solution, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain the ITO substrate.
SnO 2 Preparing a compact layer: 1mLSnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Further, the solution method comprises the following operation method: snO is treated 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Preparation of perovskite light absorption layer:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of dimethyl sulfoxide and dimethyl formamide with the volume ratio of 1:4 to obtain the solution with the concentration of 1.4mol/mL, stirring on a stirring table for 5h for full dissolution, and filtering the solution by using a 45-micron filter head to obtain the perovskite precursor solution.
2-2) taking 90 mu L ofThe perovskite precursor solution is preheated at 70 ℃ and is coated with SnO 2 Spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, dripping 150 mu l of chlorobenzene 15-20s before the spin-coating is finished, and heating on a heating table at 150 ℃ for 15min after the spin-coating.
3) Preparation of passivation layer
3-1) 20mmol of 4,5-dihydroimidazole-2-hydrazine hydroiodide powder is dissolved in 1mL of LIPA, the obtained solution is 20mmol/mL, the obtained solution is placed on a stirring table at normal temperature, the stirring is carried out for 2 hours, and after the solution is fully dissolved, a 45-micron filter head is used for filtering the solution.
3-2) dropping 90. Mu.L of the perovskite solution on the perovskite light absorption layer obtained by the step 2) which has been cooled, rotating it at 4000rpm for 30s, spin-coating, and then heating it on a heating stage at 100 ℃ for 5min.
The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 Perovskite material), a passivation layer (4,5-dihydroimidazole-2-hydrazine hydroiodide).
Example 3
1) And cutting the ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning solution, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain the ITO substrate.
SnO 2 Preparing a compact layer: 1mL of SnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Furthermore, the solution method comprises the step of carrying out SnO 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Preparation of perovskite light absorption layer:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of mixed solvent of dimethyl sulfoxide and dimethylformamide, wherein the volume ratio of dimethyl sulfoxide to dimethylformamide is 1:4, obtaining the concentration of the solution of 1.4mol/mL, stirring on a stirring table for 5h, and filtering the solution by using a 45-micron filter head to obtain the perovskite precursor solution.
2-2) taking 90 mu L of the perovskite precursor solution, dripping the solution, preheating at 70 ℃, and covering with SnO 2 And spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, dripping 150 mu l of chlorobenzene 15-20s before the spin-coating is finished, and heating on a heating table at 150 ℃ for 15min after the spin-coating.
3) Preparation of passivation layer
3-1) 30mmol of 4,5-dihydroimidazole-2-hydrazine hydroiodide powder is dissolved in 1mL IPA, the obtained solution is 30mmol/mL, the solution is placed on a normal temperature stirring table to be stirred for 2h and fully dissolved, and then the solution is filtered by a 45 mu m filter head.
3-2) dropping 90. Mu.L of the perovskite solution on the perovskite light absorption layer obtained by the step 2) which has been cooled, rotating it at 4000rpm for 30s, spin-coating, and then heating it on a heating stage at 100 ℃ for 5min. The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 Perovskite material), passivation layer (4,5-dihydroimidazole-2-hydrazine hydroiodide).
Comparative example 1
1) And cutting the ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning solution, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain the ITO substrate.
SnO 2 Preparing a compact layer: 1mL of SnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Further, the solution method comprises the following operation steps: snO 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Preparation of perovskite light absorption layer:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of mixed solvent of dimethyl sulfoxide and dimethylformamide, wherein the volume ratio of dimethyl sulfoxide to dimethylformamide is 1:4, obtaining the concentration of the solution of 1.4mol/mL, stirring on a stirring table for 5h, and filtering the solution by using a 45-micron filter head to obtain the perovskite precursor solution.
2-2) taking 90 mu L of the perovskite precursor solution, dripping the solution, preheating at 70 ℃, and covering with SnO 2 Spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, dripping 150 mu l of chlorobenzene 15-20s before the spin-coating is finished, and heating on a heating table at 150 ℃ for 15min after the spin-coating.
The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 A perovskite material).
The method is adopted to prepare ITO/SnO with a passivation layer 2 Perovskite light absorption layer/passivation layer/gold electrode layer solar cell structure
Example 4
1) Cutting ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning solution, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain an ITO substrate;
SnO 2 preparing a compact layer: 1mLSnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Furthermore, the solution method comprises the step of carrying out SnO 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Preparation of perovskite light absorption layer:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of mixed solvent of dimethyl sulfoxide and dimethylformamide, wherein the volume ratio of dimethyl sulfoxide to dimethylformamide is 1:4, obtaining the concentration of the solution of 1.4mol/mL, stirring on a stirring table for 5h, and filtering the solution by using a 45-micron filter head to obtain the perovskite precursor solution.
2-2) taking 90 mu L of the perovskite precursor solution, preheating the solution at 70 ℃, and covering the solution with SnO 2 Spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, and spin-coating150 mu l of chlorobenzene is dripped 15-20s before the end, and the mixture is heated for 15min on a heating table at 150 ℃ after spin coating.
3) Preparation of passivation layer
3-1) 10mmol of 4,5-dihydroimidazole-2-hydrazine hydroiodide powder is dissolved in 1mL of LIPA, the obtained solution is 30mmol/mL, the obtained solution is placed on a stirring table at normal temperature, the stirring is carried out for 2 hours, and after the solution is fully dissolved, a 45-micron filter head is used for filtering the solution.
3-2) dropping 90. Mu.L of the perovskite solution on the cooled perovskite light absorption layer obtained from the step 2), rotating it at 4000rpm for 30s, spin-coating, and then heating on a heating stage at 100 ℃ for 5min.
4) Preparing a hole transport layer:
preparing a spiro-OMeTAD hole transport layer: the hole transport layer solution was prepared for the first two hours of use in solvent of chlorobenzene (1mL), spiro-OMeTAD powder (72.3mg), TBP (28.8. Mu.L), liTFSI (17.5. Mu.L), and Co (III) TFSI (8. Mu.L). After the sample was cooled to room temperature, 50. Mu.L of the hole transport layer solution was dropped on the sample and spin-coated (3000 rpm, 30 s).
5) And (3) evaporating the gold electrode layer: using vacuum coating machine at 1X 10 -5 A70 nm thick gold film was deposited under Pa as an electrode.
The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 Perovskite material), passivation layer (4,5-dihydroimidazole-2-hydrazine hydroiodide), hole transport layer (spiro-OMeTAD), gold electrode layer.
Example 5
1) And cutting the ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning solution, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain the ITO substrate.
SnO 2 Preparing a compact layer: 1mL of SnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Further, the solution method comprises the following operation method: snO 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Perovskite light absorption layer preparation:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of mixed solvent of dimethyl sulfoxide and dimethylformamide, wherein the volume ratio of dimethyl sulfoxide to dimethylformamide is 1:4, obtaining the concentration of the solution of 1.4mol/mL, stirring on a stirring table for 5h, and filtering the solution by using a 45-micron filter head to obtain the perovskite precursor solution.
2-2) taking 90 mu L of the perovskite precursor solution, dripping the solution, preheating at 70 ℃, and covering with SnO 2 Spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, dripping 150 mu l of chlorobenzene 15-20s before the spin-coating is finished, and heating on a heating table at 150 ℃ for 15min after the spin-coating.
3) Preparation of passivation layer
3-1) 20mmol of 4,5-dihydroimidazole-2-hydrazine hydroiodide powder is dissolved in 1mL of IPA, the obtained solution is 30mmol/mL, the obtained solution is placed on a room temperature stirring table to be stirred for 2 hours and fully dissolved, and then the solution is filtered by a 45 μm filter head.
3-2) dropping 90. Mu.L of the perovskite solution on the cooled perovskite light absorption layer obtained from the step 2), rotating it at 4000rpm for 30s, spin-coating, and then heating on a heating stage at 100 ℃ for 5min.
4) Preparing a hole transport layer:
preparing a spiro-OMeTAD hole transport layer: the hole transport layer solution was prepared for the first two hours of use in solvent of chlorobenzene (1mL), spiro-OMeTAD powder (72.3mg), TBP (28.8. Mu.L), liTFSI (17.5. Mu.L), and Co (III) TFSI (8. Mu.L). After the sample was cooled to room temperature, 50. Mu.L of the hole transport layer solution was dropped on the sample and spin-coated (3000 rpm, 30 s).
5) And (3) evaporating the gold electrode layer: using a vacuum coating machine at 1 x 10 -5 A70 nm thick gold film was deposited under Pa as an electrode.
The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light-absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 Perovskite material), passivation layer(4,5-dihydroimidazole-2-hydrazine hydroiodide), a hole transport layer (spiro-OMeTAD), and a gold electrode layer.
Example 6
1) Cutting the ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning liquid, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain the ITO substrate.
SnO 2 Preparing a compact layer: 1mLSnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Furthermore, the solution method comprises the step of carrying out SnO 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Preparation of perovskite light absorption layer:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of mixed solvent of dimethyl sulfoxide and dimethylformamide, wherein the volume ratio of dimethyl sulfoxide to dimethylformamide is 1:4, obtaining the concentration of the solution as 1.4mol/mL, stirring on a stirring table for 5h to fully dissolve, and filtering the solution by using a 45-micron filter head to obtain the perovskite precursor solution.
2-2) taking 90 mu L of the perovskite precursor solution, preheating the solution at 70 ℃, and covering the solution with SnO 2 Spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, dripping 150 mu l of chlorobenzene 15-20s before the spin-coating is finished, and heating on a heating table at 150 ℃ for 15min after the spin-coating.
3) Preparation of passivation layer
3-1) 30mmol of 4,5-dihydroimidazole-2-hydrazine hydroiodide powder is dissolved in 1mL of LIPA to obtain a solution of 30mmol/mL, the solution is placed on a stirring table at normal temperature and stirred for 2 hours to be fully dissolved, and then the solution is filtered by a 45-micron filter head.
3-2) dropping 90. Mu.L of the perovskite solution on the perovskite light absorption layer obtained by the step 2) which has been cooled, rotating it at 4000rpm for 30s, spin-coating, and then heating it on a heating stage at 100 ℃ for 5min.
4) Preparing a hole transport layer:
preparing a spiro-OMeTAD hole transport layer: the hole transport layer solution was prepared for the first two hours of use in solvent of chlorobenzene (1mL), spiro-OMeTAD powder (72.3mg), TBP (28.8. Mu.L), liTFSI (17.5. Mu.L), and Co (III) TFSI (8. Mu.L). After the sample was cooled to room temperature, 50. Mu.L of the hole transport layer solution was dropped on the sample and spin-coated (3000 rpm, 30 s).
5) And (3) evaporating the gold electrode layer: using a vacuum coating machine at 1 x 10 -5 A70 nm thick gold film was deposited under Pa as an electrode.
The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 Perovskite material), passivation layer (4,5-dihydroimidazole-2-hydrazine hydroiodide), hole transport layer (spiro-OMeTAD), gold electrode layer.
The method is adopted to prepare ITO/SnO without a passivation layer 2 Perovskite light absorption layer/gold electrode layer solar cell structure
Comparative example 2
1) Cutting the ITO conductive glass into the size of 25mm multiplied by 25mm, respectively washing the ITO conductive glass with conductive glass cleaning liquid, deionized water and ethanol, putting the ITO conductive glass into an oven for drying, and carrying out UV surface treatment to obtain the ITO substrate.
SnO 2 Preparing a compact layer: 1mLSnO 2 Diluting colloidal dispersion liquid by 7 times with deionized water to obtain SnO 2 And (3) solution. Furthermore, the solution method comprises the step of carrying out SnO 2 Depositing the precursor solution on the ITO substrate; the annealing temperature is 150 ℃, and the annealing time is 40min.
2) Preparation of perovskite light absorption layer:
2-1) weighing 1.33mol of formamidine hydroiodide, 0.07mol of methyl ammonium bromide, 1.4mol of lead iodide and 0.07mol of lead bromide, dissolving in 1mL of mixed solvent of dimethyl sulfoxide and dimethylformamide, wherein the volume ratio of dimethyl sulfoxide to dimethylformamide is 1:4, obtaining the concentration of the solution of 1.4mol/mL, stirring on a stirring table for 5h, and filtering the solution by using a 45-micron filter head to obtain the perovskite precursor solution.
2-2) taking 90 mu L of the perovskite precursorThe solution drops are coated with SnO preheated at 70 DEG C 2 Spin-coating the ITO substrate with the dense layer at 1000rpm for 10s, spin-coating at 4500rpm for 30s, dripping 150 mu l of chlorobenzene 15-20s before the spin-coating is finished, and heating on a heating table at 150 ℃ for 15min after the spin-coating.
3) Preparing a hole transport layer:
preparing a spiro-OMeTAD hole transport layer: the hole transport layer solution was prepared for the first two hours of use in solvent of chlorobenzene (1mL), spiro-OMeTAD powder (72.3mg), TBP (28.8. Mu.L), liTFSI (17.5. Mu.L), and Co (III) TFSI (8. Mu.L). After the sample is cooled to room temperature, 50 mu L of hole transport layer solution is dripped on the sample for spin coating (3000 rpm, 30 s);
4) And (3) evaporating the gold electrode layer: using vacuum coating machine at 1X 10 -5 A70 nm thick gold film was deposited under Pa as an electrode.
The prepared device comprises an ITO substrate and SnO from bottom to top 2 Dense layer (i.e., electron transport layer), perovskite light absorbing layer ((FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 Perovskite material), hole transport layer (spiro-OMeTAD), gold electrode layer.
The invention compares the products obtained in examples 1 to 3 with the product obtained in comparative example 1 and explores the effect of the passivation layer
The X-ray diffraction test was performed on the perovskite film in which 4,5-dihydroimidazole-2-hydrazine hydroiodide was added as a passivation layer in example 2 and the standard perovskite film without a passivation layer prepared in comparative example 1, and the results obtained are shown in fig. 2. As is evident from the X-ray diffraction patterns of the standard sample and the passivated sample, the passivation treatment of 4,5-dihydroimidazole-2-hydrazine hydroiodide does not change the bulk perovskite structure, and the standard sample has PbI near 12.7 DEG 2 Characteristic peaks, however, 4,5-dihydroimidazole-2-hydrazine hydroiodide reacts with the remaining PbI in the perovskite after passivation treatment 2 Reaction takes place, leading to PbI 2 The characteristic peak intensity is obviously reduced, a new diffraction peak appears near 4.9 degrees, which represents that a new low-dimensional phase is formed on the surface of the blocky perovskite and is consistent with a low-dimensional perovskite phase formed when the molar ratio of 4,5-dihydroimidazole-2-hydrazine hydroiodide to lead iodide is 2:1.
Fig. 3 shows scanning electron microscope images of the surface of the perovskite thin film treated with the passivation layer of 4,5-dihydroimidazole-2-hydrazine hydroiodide (right picture) and without (left picture), from which it is apparent that the thin film without the passivation layer shows a dense surface but clearly visible grain boundaries, while the thin film with the passivation layer of 4,5-dihydroimidazole-2-hydrazine hydroiodide shows a smoother, denser, more uniform surface with fewer grain boundaries, which is in favor of efficient charge transfer and excellent photovoltaic performance.
FIG. 4 shows UV-vis absorption spectra of various concentrations of 4,5-dihydroimidazole-2-hydrazine hydroiodide for passivation and standard perovskite films, where the light absorption capacity of the passivated films is slightly enhanced, which correlates to the increase in short-circuit current density for various concentrations of 4,5-dihydroimidazole-2-hydrazine hydroiodide in Table 1 for passivation and standard perovskite devices.
The invention is compared with the products prepared in comparative example 2 and examples 4 to 6:
FIG. 5 and Table 1 show different concentrations of 4,5-dihydroimidazole-2-hydrazine hydroiodide as passivation layer treatments and standard perovskite solar cells at standard AM1.5G (100 mW. Cm) -2 ) And recording the J-V curve of the perovskite solar cell and corresponding photovoltaic parameters under illumination. Enhanced photoelectric conversion efficiency is obtained by optimizing the concentration of the passivation layer used in the perovskite film preparation process.
(FAPbI 3 ) 0.95 (MAPbBr 3 ) 0.05 Current density (J) of thin-film and passivation-layer-treated perovskite solar cells sc ) From the original 24.54mA cm -2 Lifting to 25.08mA cm -2 Open circuit voltage (V) oc ) The photoelectric conversion efficiency is improved from 20.46% to 23.09% and the Fill Factor (FF) is improved to 78.95%, the photoelectric performance is obviously improved, and in conclusion, the treatment of the passivation layer (FAPBI) improves the photoelectric conversion efficiency from 1.08V to 1.16V 3 ) 0.95 (MAPbBr 3 ) 0.05 The film is applied to the field of solar cells, and the matching and addition effects are exerted to a great extent.
Table 1 influence of passivation layer on solar cell performance
From the above embodiments, it can be seen that, according to the present invention, by depositing the halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazinehydrogen) on the interface between the perovskite light absorption layer and the hole transport layer, the surface defects of the perovskite light absorption layer are passivated, non-radiative recombination can be inhibited, and interface charge extraction can be improved, so as to improve device efficiency and stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A perovskite solar cell comprises an ITO substrate and SnO which are arranged in sequence 2 The electron transport layer, the perovskite light absorption layer, the passivation layer, the hole transport layer and the gold electrode layer;
the passivation layer is a halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazine hydrogen).
2. The perovskite solar cell of claim 1, wherein the passivation layer is one or more of 4,5-dihydroimidazole-2-hydrazine hydroiodide species, 4,5-dihydroimidazole-2-hydrazine hydrobromide species, and 4,5-dihydroimidazole-2-hydrazine hydrochloride species.
3. The perovskite solar cell of claim 1, wherein the perovskite light absorption layer is made of a material (FAPbI) 3 ) 0.95 (MAPbBr 3 ) 0.05 。
4. The perovskite solar cell of claim 1, wherein SnO 2 Electronic transmissionThe thickness of the layer is 20-30 nm;
the thickness of the perovskite light absorption layer is not less than 100nm;
the thickness of the passivation layer is 5-20 nm;
the thickness of the hole transport layer is 150-220 nm;
the thickness of the gold electrode layer is 65-85 nm.
5. A method of manufacturing a perovskite solar cell as defined in any one of claims 1 to 4, comprising the steps of:
deposition of SnO on ITO substrates 2 Precursor solution is annealed to obtain SnO 2 An electron transport layer;
coating perovskite precursor solution on SnO in a spinning mode 2 Heating the electron transmission layer to obtain a perovskite light absorption layer;
then spin-coating a passivation layer solution on the perovskite light absorption layer and heating to obtain a passivation layer, wherein the passivation layer is a halogen salt substance containing heterocyclic ammonium salt cations (4,5-dihydroimidazole-2-hydrazine hydrogen);
spin-coating a hole transport layer solution on the passivation layer to obtain a hole transport layer;
and preparing a metal electrode layer on the hole transport layer by using a vacuum evaporation method to obtain the perovskite solar cell.
6. The method according to claim 5, wherein the passivation layer solution is used in an amount of 15 to 25 μ L/cm 2 ；
The rotating speed of the spin-coating passivation layer solution is 3000-5000 rpm;
the temperature for heating the passivation layer solution is 90-120 ℃, and the time for heating the passivation layer solution is 5-10 min.
7. The production method according to claim 5, wherein the amount of the perovskite precursor solution used is 15 to 25 μ L/cm 2 The rotating speed of spin coating is 3000-5000 rpm;
the temperature for heating the perovskite precursor solution is 120-150 ℃ and the time is 10-15 min.
8. The preparation method according to claim 5, wherein the concentration of the halogen salt species containing heterocyclic ammonium salt cation (4,5-dihydroimidazole-2-hydrazinehydrogen) in the passivation layer solution is 10 to 50mmol/mL; the solvent in the passivation layer solution is isopropanol;
the concentration of the perovskite precursor solution is 1.4-1.8 mol/mL; the perovskite precursor solution is an organic mixed solvent of a dimethyl sulfoxide solvent and a dimethyl formamide solvent, and the volume of the dimethyl formamide solvent in each unit volume of the organic mixed solvent is 4-9 times of that of the dimethyl sulfoxide solvent.
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